Process for imparting a soft handle to textile materials and aqueous dispersions suitable therefor

ABSTRACT

892,167. Aqueous polyalkylene polyamine dispersions. CIBA Ltd. June 15, 1960 [June 16, 1959], No. 21067/60. Class 1(1) [Also in Groups IV(b) and IV(c)] Aqueous dispersions of compounds of formula in which A represents an alkylene radical containing 2 or 3 carbon atoms, K an aliphatic hydrocarbon residue containing 13 to 21 carbon atoms and m and n are whole numbers being at most 3 and 2 respectively are used to treat textile materials there being present at least partially a compound in which n=2. In an example an aqueous solution containing an adduct of ethylene oxide and hydroabietyl alcohol, an adduct of ethylene oxide and oleyl alcohol and a condensation product neutralized with sodium hydroxide solution of naphthalene sulphamic acid and formaldehyde is heated and stirred in an open vessel. To this solution is then added aqueous ammonia and a melt consisting of ethylene glycol monoethyl ether, stearic acid and the condensation product consisting of diethylene triamine and stearic acid, the rate of stirring increasing during addition until a smooth dispersion is obtained. The dispersion is diluted with hot water homogenized and cooled. Other examples describe the preparation of dispersions as above but containing condensation products from (1) diethylene triamine and myristic, palmitic or behenic acids instead of stearic acid and (2) stearic acid and triethylene tetramine, or tetraethylene pentamine instead of diethylene triamine. The dispersions may contain solvents in addition to water, e.g. xylene, decalin, chlorobenzene, o-dichlorobenzene, benzyl chloride, trichloroethylene and mono- and diethylene glycol monoethyl ether. As non-ionic dispersants the dispersions may contain adducts of ethylene oxide with (1) oleyl alcohol (2) oleylamine (3) hydroabietyl alcohol and (4) hydrogenated abietylamine. Alternatively the dispersions may contain an adduct of ethylene oxide and hydroabietyl alcohol cross linked with (1) hexamethylene drisocyanate or (2) diphenyl methane drisocyanate or an adduct of ethylene oxide and oleyl alcohol cross linked with hexamethylene drisocyanate.

are present. I terminal ones, may also contain alkyl groups instead ofUnited States Patent especially of compounds of the formula in which Arepresents a lower alkylene radical; R a higher aliphatic hydrocarbonradical, and m and n represent whole numbers, in being at most=3 and nat most=2, there being present at least partially a compound of thisformula in which n=2.

The present process can of textile materials.

be applied to a wide variety As examples may be mentioned:

Natural fibers of animal origin, such as wool or silk,

Natural fibers of vegetable origin, more especially cellulose fiberssuch as cotton or linen,

Semi-synthetic fibers, for example of cellulose ethers or celluloseesters such as cellulose nitrate or cellulose acetate, among whichcellulose triacetate deserves to be mentioned especially,

Fully synthetic fibers, for example of polyacrylonitrile, polyurethane,polyamides of e-caprolactam or of adipic acid and hexamethylene diamine,polyester fibers, more especially of terephthalic acid polyglycol ester.

It is of course also possible to treat fibers of copolymers orco-condensates as well as blended fibers, for example of natural andsynthetic fibers such as wool and polyarnide, wool andpolyacrylonitrile, or wool and polyester fibers. The fiber material canbe treated at any stage of its processing, for example in the form ofloose fibers, hanks, yarn, woven or knitted fabrics.

In this connection the term polyalkylene polyamines acylated withradicals of higher carboxylic acids refers to acyl derivatives ordialkylene triamines, trialkylene tetramines and higher polyamines mostof whose nitrogen atoms carry acyl groups. At least an essential portionfor example at least 20%, of the product used in the present process,should consist of an acyl compound or compounds, all acylatable nitrogenatoms of which contain acyl groups so that in the portion consisting ofthis compound or these compounds no basic nitrogen atoms Some nitrogenatoms, more especially the or preferably in addition to acyl groups.

Thus, the acyl compounds to be used in the present process maycorrespond, for example, to the general formula f I m+n TiT iZ Fr inwhich A stands for a lower alkylene radical, R for a higheraliphatichydrocarbon radical, m, n, p' and q are whole numbers, in beingat most=3 and n at most:2, there being present at least partially acompound in which 11:2. i i

Preferred use is made of compounds of the Formula 1, which containpolyalkylene polyamine radicals of the composition l Um I in which Astands for a lower alkylene radical, for example a propylene radical(-CH CH CH or preferably for an ethylene radical (-CH --CH and m=1, 2 or3. Accordingly, the compounds of the Formula 1 are derivatives ofdialkylenetriamines (m=l), trialkylenetetramines (111:2) ortetraalkylenepentamines The acyl compounds of the Formulae l and 2. canbe prepared from suitable amines of the formulae (5) (H C 9-HN {-ANH}ANH- C H in which A, m, p and q have the above meanings-by reaction witha carboxylic acid of the formula HOOCR in which R represents a higheraliphatic radical. It is of advantage to use a saturated higher fattyacid of the formula in which r is a whole, preferably even, number from12 to 20, thus, for example myristic, palmitic, stearic, arachidic orbehenic acid. It is by no means necessary to subject the polyamine to aunitary acylation; in fact the acylation can be performed very well witha mixture of higher fatty acids, for example mixtures of difierent fattyacids of the Formula 7 which may also contain a certain share ofunsaturated acids, such as oleic acid. [This applies equally to theFormulae 1 and 2; that is to say the radicals OCR present in a moleculeof these compounds need not all be identical.] Thus, the acylation canbe carried out, inter alia, with so-called commercial stearic acid whichconsists substantially of stearic acid and contains also other higherfatty acids, more especially palmitic acid and a small amount of oleicacid and Whose average molecular weight is about 270.

To achieve the extensive acylation required it is in general necessaryto heat the polyamines together with the carboxylic acid for a prolongedperiod at an elevated temperature. It is of advantage to raise thetemperature gradually, for example, the reaction mixture is first heatedfor several hours at a temperature of about l40l70 C. and then likewisefor several hours at a temperature of 299-250 C. Even when the molecularratio polyaminezacid is selected so that for each basic nitrogen atomone acid molecule is available (that is to say for example 3 mols ofstearic acid for 1 mol of diethylenetriamine, or a slight excess ofstearic acid over and above 3 mols) the product obtained as 'a rule iseven under the above-mentionedenergetic conditions not a unitary,completely acylated polyamine but a mixture which contains in additionto completely acylated amine, forexample triacyl-diethylenetriamine ortetraacetyl-triethylenetetraamine, a considerable share of amine saltformed from carboxylic acid and amine that has'not yet been completelyacylated so that it is still basic.- i

The resulting acyl compounds to be used in the present process have ingeneral a melting point of over C. and an appearance which resemblesthat of a hard wax. The preparation of fine, smooth and stabledispersions ofthese compounds in water, such as arerequired in thepresent process, is not a very simple matter.

dispersant, more especially a polyglycol compound which may be derived,for example, from a higher amine or alcohol and contains advantageouslya relatively long chain of -CH CH --O groups, for example a chainconsisting of 50 to 250 such groups.

Mixtures of such non-ionic dispersants are likewise suitable. Thus, forexample, good results are achieved by using an adduct of about 60 to 100mols of ethylene oxide with a higher alcohol, such as oleyl alcohol, ora higher fatty amine, such as oleylamine, and additionally an adduct ofabout 150 to 250 mols of ethylene oxide with a higher alcyclic alcoholor amine, such as hydroabietyl alcohol or hydroabietylamine.

Since the acyl compounds used in the preparation of the aqueousdispersions as a rule melt above 100 C., and this preparation isfacilitated or even made possible only when the acyl compounds in theliquid state can be brought into the requisite fine dispersion in water,it is of advantage to add to the acylamino compounds before theirdispersion a substance that causes their melting point to drop below 100C. This enables the liquid acyl compounds to be dispersed in water, atleast when Warm or hot water is used. Substances suitable for loweringthe melting point are above all inert organic solvents having a highboiling point such, for example, as xylenes or mixtures of xylenes,decahydronaphthalene, chlorobenzene, diehlorobenzenes, benzyl chloride,trichloroethylene, glycol monoethyl ether or diglycol monoethyl ether.

The dispersions to be used in the present process may also containfurther substances, for example nitrogenous bases such as ammonia,higher fatty acids such as stearic acid, or the corresponding salts. Itis of special advantage to perform the process in the presence of ananionactive dispersant, as which may be mentioned more especiallycondensation products of naphthalenesulfonic acids with formaldehyde.

The amounts of substances contained in the dispersion may vary withinwide limits. It will be readily understood that, apart from water, theactive principle proper, that is to say the acyl compound, shouldpreponderate in these dispersions. The substances which reduces themelting point should be used in a rather smaller amount thoughadvantageously still of the same order. For example: 20-100 parts ofsuch a substance are used for every 100 parts of acyl compound. Theamount of nonionic and if desired anion-active dispersants used shouldbe for example 560% of the weight of the acyl compound. When thedispersion is to be used for triacetate or polyester fibers it shouldcontain in addition to a nonionic dispersant also at least oneanion-active dispersant in an amount of 0.5l0% of the weight of the acylcompound present.

The dispersion is prepared for example as follows:

A melt containing the acyl compounds, the substance that reduces themelting point and if desired further substances such as free fatty acid,and whose temperature is at most about 100 C., is stirred into a hotaqueous solution containing the non-ionic dispersant or dispersants andany other dissolved substances, for example the anionactive dispersant,rapid and thorough mixing being ensured, for example, with a high-speedstirrer. Alternatively, the anion-active dispersant can be addedsubsequently. By adding water, advantageously while the reaction mixtureis still warm, the dispersion can be adjusted to a specific strength.

The resulting dispersions have good stability and can be diluted to thedesired strength with cold or at least with hot water. These baths canbe used to treat the textile materials in the conventional manner.Depending on the fiber material concerned it may be of advantage totreat it at a higher or lower temperature. Thus, for example, thefollowing treatment temperatures are suitable: Wool or polyarnide fibers-30 C.; cotton 2040 C.; polyacrylonitrile and cellulose triacetate at3060 C.; polyester fibers with advantage 90l00 C.

However, these temperatures are simply examples, and in a given casegood results may also be achieved at other temperatures. The amount isselected for example so that at the usual goods-to-liquor ratio of 1:20to 1:40, the amount of (concentrated) dispersion added is such that thebath contains about 0.1 to 2% (calculated on the weight of the fibermaterial) of acyl compounds. In general it is of advantage to add anacid, more especially formic acid. The treatmentmore especially when itis carried out at a low temperatureshould not be discontinued too soonand should be performed, for example, for 15 minutes to 2 hours. Thisensures the fixation of the acyl compounds on the fiber material and agood and lasting soft handle is imparted to the latter.

Unless otherwise indicated, parts and percentages in the followingexamples are by weight.

EXAMPLE 1 A. Manufacture of the Acyl Compounds A mixture of 103 parts (1mol) of diethylenetriamine and 810 par-ts (3 mols) of commercial stearicacid having a molecular Weight of 270 is slowly heated to to C. Whilebeing stirred under nitrogen. When this temperature has been reached,the melt foams only little. After another 3 hours the melt is heated toto C. and this temperature is maintained for 4 /2 hours. After cooling,there are obtained about 861 parts of a brittle, pale-yellow, waxysubstance which melts at 93-94 C. and, as revealed by titration with 0.1N-perchloric acid in glacial acetic acid, still contains 0.6 gram atomof basic nitrogen. The content of free stearic acid, calculated from theacid number of 38.2, is 0.59 mol (condensation product No. l).

The condensation product No. 1 obtained in the manner described above isheated for another 18 hours at 215220 C. The content of free stearicacid, calculated from the acid number of 13.45, is 0.15 mol. A brittle,

Waxy substance melting at 98 to 100 C. is obtained (condensation productNo. 2).

B. Preparing the Dispersion The apparatus used is an open stirringvessel equipped with a blade stirrer of stainless steel which has astrong downward beating action towards the bottom of the vessel and thespeed of which can be raised to 6000 revolutions per minute. A solutionheated to at least 90 C., containing 1.5 parts of an .adduct of 200 molsof ethylene oxide and 1 mol of hydroabietyl alcohol; 0.75 part of anadduct of 80 mols of ethylene oxide and 1 mol of oleyl alcohol; 0.75part of a condensation product, neutralized with aqueous sodiumhydroxide solution, of naphthalene sulfonic acid and formaldehyde, and20 parts of water is K caused by stirring to circulate in theaforementioned apparatus. There are then added to the solution 2.5 partsof aqueous ammonia of 25% strength and then 12.5 parts of a melt heatedto at least 95 C. of 2.5 parts of ethylene glycol monoethyl ether, 1pant of stearic acid and 9 parts of the condensation product of 1 mol ofdiethylene triamine and 3 mols of stearic acid prepared as describedabove under A (condensation product No.

2) at a rate such that the added melt is immediately absorbed. Whilepouring in the melt the speed of the stirrer, which initially isrelatively low, must be continually increased. On completion of theaddition the mixture is stirred very rapidly until a smooth dispersionhas been obtained. Another 62 parts of water of condensation having atemperature 70 C. are then added and the stirrer is considerably sloweddown. The hot dispersion is then adjusted with hot water to a weight of100 parts, again homogenized for a short time and then left to itselfuntil it has cooled completely. A very thinly liquid, highly colloidaldispersion is obtained which is very easy to filter. It can be dilutedwith hot or with cold water.

In an identical manner a dispersion can be prepared from condensationproduct No. 1.

C. Finishing of the Fiber Material (a) Polyacrylonitrile fibers-100parts of polyacrylonitrile fiber yarn are treated for minutes at C. with5000 parts of a liquor containing 1 to 2 parts of the dispersiondescribed under B above and 3 parts of concentrated formic acid. Afterhaving been centrifuged and dried at about 60 C., the yarn has a softhandle.

Number 1 2 3 4 5 A. Condensation product prepared from 1 moldiethylenetriamine+3 mols stearic acid:

Asin Ex. 1 A, para. 1 18 As in Ex. 1 A, para. 2 9 10 9 9 18 18 18 18 1818 18 18 18 Analogous cond. prods. prepared as in Ex. 1A, para. 2 from:

1 mol diethylenetriamine+3 mols m 'stic acid 1 mol diethylenetriamine+3mols palrnitio acid 1 mol diethylenetriaznine+3 mols behenic acid 1 moltriethylenetetramine+4 mols stearic acid 1 moltetracthylcnepentamine-l-fi mols stearic acid Ethylene'di-stearoylamidePhenylene-di-stearoylamide Stearic acid Solvent:

Xylene Decalin Chlorobenzene o-Dichlorobenzene.. Benzyl chloride.Trichloroethylcno- Ethylene glycol mono y Dicthylcne glycol monoethylether C. Non-ionic dispersants, Adduct of:

80 mol; ethylene oxide-H mol oleyl CO sfil mols ethylene oxide+1 mololey amine 1.5. 3 200 mols ethylene oxide-H mol hydroabietyl alcohol 1.51 5 3 6 6 6 6 6 6 6 6 6 6 6 6 3 200 mols ethylene oxide- 1 molhydrogenatcd abietylarniue 6- D. Anion-active dispersant: Neutral- 1ized eond. prod. of naphthalenesulionic and and formaldehyde 0.75 0.751.2 1.2 1.2 1.2 1.2 1 2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2

(b) Celiulose triacetale fibers-Cellulose triacetate EXAMPLE 3 fiber 15F as described above under where If the adduct of 200 mols of ethyleneoxide and 1 mol upon E Z g f am i f bri of of hydroabietyl alcohol inthe dispersion of columns 1 t g g y f :5 01 2:: g 'i a g; to and 3 inExample 2 is replaced by the same quantity of ig' g i g j i bathcontaining in 3000 (a) An adduct of 200 mols of ethylene oxide and 1 molI p of hydroabietyl alcohol, crosslinkedwith about 1% of water 2 to 4parts of the dispersion descnbed above of hexamethylgne diisocyanate orgg a a gg gg f g g (b) An adduct @1100 mols of ethylene oxide and 1 molcan an s d1 6 e m of hydmabietyI. alcohol, cross-linked with about.1.5%d C0 :30: 1 1 1 11511 c t on arn is treated at 25 C of diphenylmethanediisqcyhnatei or (0) An adduct of -80 mols of ethylene oxide and 1 molabwe under (a), a Sm handle orcie i alcohol. cross-linked with about 1%hexa Without having turned yellow. methylenrdfisocynat, r

p i g ggfj fig g 9 g g of very stable highly colloidal emulsions areobtained, hay- P Y tram 9r mmu es a a ing a hig herfyiscosifi than thecorresponding ones debath containing in 3000 parts 2 to 4 parts of thedis- Sribed-in Example-2 persion described above under B and 3 parts ofcon- What is i V centrated formic acid, it displays a sott handle. Inthe Probessior imparting a Soft handle to textile m g Sgfihandle canalso be ImPaIted to .terials which comprises vtreating the materialswith an (f) 00 EXAMPLE 2 aqueous dispersion of a mixture of compounds ofthe formulae The condensation products Nos. 3 to 19 listed under (a)CPR) A in the following tablecan be prepared as, described T fin-Example 1 under A for condensation product No. 2. Y T T By the methoddescribed under 13 in Example 1 stable 7 dispersions can be preparedfrom the resulting condenand sation products with the use of thesolventslisted in the (b) p table under B (Example 1: Ethylene glycolmonoethyl f I ether), of the non-ionic dispersant (Example 1: Adduot ofethylene oxide and oleyl alcohol, and .adduct of ethylin which Arepresents a lower alkylene radical, R a higher aliphatic hydrocarbonradical, and m is a whole number of at most 3, the'compound of Formula abeing present in an amount of at least 20% and in an eifective amount.

2. Process for imparting a soft handle to textile materials whichcomprises treating the materials with an aqueous dispersion of a mixtureof compounds of the formulae in which R represents a higher aliphatichydrocarbon radical, and m is a whole number of at most 3, the compoundof Formula a being present in an amount of at least 20% and in aneffective amount in said mixture.

3. Process for imparting a soft handle ,to textile mate rials whichcomprises treating the materials with an aqueous dispersion of a mixtureof compounds of the formulae and and

in which m and r are whole numbers, m being at most=3, r at least= 12and at most=20, the compound of Formula a being present in an amount ofat least 20% and in an efiective amount, and a non-ionic dispersant.

5. Process for imparting a soft handle to textile materials whichcomprises treating the materials with an aqueous dispersion of a mixtureof compounds of the formulae and 1 CH [HN CHrCHrN CHrCHrIP HJi: 0C \0 73 m-H 1 1 PH] in which m and r are whole numbers, m being at most=3, rat least=l2 and at most=20, the compound of Formula a being present inan amount of at least 20% and in an in which m and r are whole numbers,m being at most=3, r at least=l2 and at most=20, the compound of Formulaa being present in an amount of at least 20% and in an effective amount,dispersing agents of the aqueous dispersion being an adduct of ethyleneoxide and a higher alcohol as a non-ionic dispersant and a condensationproduct of naphthalene sulfonic acid and formaldehyde as an anion-activedispersant, the latter in an amount of from 0.5 to 10% by Weight of themixture of compounds (a) and (b).

7. Process for imparting a soft handle to textile materials whichcomprises treating the materials with an aqueous dispersion of a mixtureof compounds of the formulae and the compound of Formula a being presentin an amount of at least 20% and in an effective amount, dispersingagents of the aqueous dispersion being an adduct of ethylene oxide and ahigher alcohol as a non-ionic dispersant and a condensation product ofnaphthalene sulfonic acid and formaldehyde as an anion-activedispersant, the latter in an amount of from 0.5 to 10% by weight of themixture of compounds a and b.

8. An aqueous dispersion suitable for imparting a soft handle to textilematerials, of a mixture of compounds of the formulae [ar W u] in which Arepresents a lower alkylene radical, R a higher aliphatic hydrocarbonradical, and m is a whole number of at most 3, the compound of Formula abeing present in an amount of at least 20% and in an eifective amount.

9. An aqueous dispersion suitable for imparting a soft handle to textilematerials, of a mixture of compounds of the formulae and soft handle totextile materials, of a mixture of compounds of the formulae in which mand r are whole numbers, m being at most 3, r at least: 12 and atmost=20, the compound of Formula a being present in an amount of atleast 20% and in an efiective amount.

11. An aqueous dispersion suitable for imparting a soft handle totextile materials, of a mixture of compounds of the formulae and inwhich m and r are whole numbers, m being at most=3, r at least=l2 and atmost=20, the compound of Formula a being present in an amount of atleast 20% and in an effective amount in said mixture, dispersing agentsof the aqueous dispersion being a non-ionic dispersant and ananion-active dispersant, the latter in an amount of from 0.5 to 10% byweight of the mixture of compounds (a) and (b).

13. An aqueous dispersion suitable for imparting a soft handle totextile materials, of a mixture of compounds of the formulae in which mand r are whole numbers, m being at most=3, r at ieast=12 and atmost-=20, the compound of Formula a being present in an amount of atlast 20% and in an effective amount, dispersing agents of the aqueousdispersion being an adduct of ethylene oxide and a higher alcohol as anon-ionic dispersant and a condensation product of naphthalene sulfonicacid and formaldehyde as an anion-active dispersant, the latter in anamount of from 0.5 to 10% by weight of the mixture of compounds (at) and(b).

14. An aqueous dispersion, suitable for imparting a soft handle totextile materials, of a mixture of compounds of the formulae and inwhich mixture the compound of Formula a is present in an amount of atleast 20% and in an efiective amount, an adduct of ethylene oxide and ahigher alcohol as a nonionic dispersant and a condensation product ofnaphthalene sulfonic acid and formaldehyde as an anion-activedispersant, the latter in an amount of from 0.5 to 10% by Weight of themixture of compounds (a) and (b).

References Cited in the file of this patent UNITED STATES PATENTS2,201,041 Katz May 14, 1940 2,213,477 Steindorf et al. Sept. 3, 19402,340,881 Kelley Feb. 8, 1944 2,345,632 Robinson et al. Apr. 4, 19442,626,876 Carnes Ian. 27, 1953 2,734,830 Hagge et a1 Feb. 14, 1956 OTHERREFERENCES Soap and Chemical Specialties, January 1958, page 49.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,131,147 April 28, 1964 Armin Hiestand It is hereby certified thaterror appears in the above numbered patent requiring correction and thatthe said Letters Patent shoul d read as corrected below.

Column 8, lines 9 to 13, the 1efthand side of the formula reading:

1' I [m ca CH N n read [m vica CH 1 lines 53 to 57, for that portion ofthe formula reading:

same column 8, lines 72 to 75, column 9, lines 2 to 5, and

' lines 14 to 17, in the right-hand side of each of the formulae forthat portion reading:

Signed andsealed this 16th day of March 1965.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner ofPatents

1. PROCESS FOR IMPARTING A SOFT HANDLE TO TEXTILE MATERIALS WHICHCOMPRISES TREATING THE MATERIALS WITH AN AQUJEOUS DISPERSION OF AMIXTURE OF COMPOUNDS OF THE FORMULAE (A) -(NH-(A-N(-))M-A-NH)--(CO-R)(M+2) AND (B) -(NH-(A-N(-))M-A-NH)- -(H) -(CO-R)(M+1) IN WHICH AREPRESENTS A LOWER ALKYLENE RADICAL, R A HIGHER ALIPHATIC HYDROCARBONRADICAL, AND M IS A WHOLE NUMBER OF AT MOST 3, THE COMPOUND OF FORMULA ABEING PRESENT IN AN AMOUNT OF AT LESS 20% AND IN AN EFFECTIVE AMOUNT.